Process for the manufacture of a multilayer material sheet, multilayer material sheet and use hereof

ABSTRACT

Multilayer material sheets containing unidirectional high performance fibers are obtained by a process which includes the steps of positioning the fibers in a parallel fashion, consolidation of the fibers to obtain a monolayer, stacking at least two monolayers such that the fiber direction in one monolayer is at an angle a to the direction of the fibers in an adjacent monolayer and fixation whereby the stack of at least two monolayers is subjected to a pressure and temperature treatment for a duration of a least 2 seconds, followed by cooling the stack under pressure to a temperature of 120° C. or lower. The multilayer material sheet has a reduced uptake of liquids.

This application is a continuation of commonly owned copending U.S.application Ser. No. 13/515,936, filed Sep. 4, 2012, which is thenational phase application under 35 USC § 371 of PCT/EP2010/069939,filed Dec. 16, 2010 which designated the U.S. and claims the benefit ofpriority of EP 09179673.0, filed Dec. 17, 2009, the entire contents ofeach of which are hereby incorporated by reference.

The present invention relates to the manufacture of a multilayermaterial sheet, the multilayer material sheet itself, and the use hereofin anti ballistic application.

A process for the manufacture of a multilayer material sheet is knownfrom EP-A-0191 306. This document discloses in one of the examples thealignment of unidirectional high strength polyethylene fibers andimpregnating the fibers with 27.3 wt % of a solution of Kraton elastomerin dicholoromethane as solvent. The obtained sheets were made on a drumwinder, typically resulting in sheets with a length/width ratio of lessthen 2.

When the multilayer material sheets manufactured with the processaccording to the prior art are contacted with liquids a certain uptakeof these liquids may occur. Such could be the case when cleaning abullet resistant vest with e.g. a liquid detergent; another case may bewhere a ballistic resistant product is contacted with e.g. kerosene orwater. High liquid uptake of a multilayer material sheet is notpreferred.

Object of the invention therefore is to provide a process for themanufacture of a multilayer material sheet with a lower uptake of liquidthan the known multilayer material sheets.

This object is obtained through a process for the manufacture of amultilayer material sheet comprising unidirectional high performancefibers, the process comprising the steps of:

-   -   a. positioning the fibers in a parallel fashion,    -   b. consolidation of the fibers to obtain a monolayer,    -   c. stacking at least two monolayers such that the fiber        direction in one monolayer is at an angle α to the direction of        the fibers in an adjacent monolayer,    -   d. fixation whereby the stack of at least two monolayers is        subjected to a pressure and temperature treatment        -   characterized in that the duration of the pressure treatment            is a least 2 seconds at a pressure of at least 0.5 MPa at a            temperature below the melting point or degradation            temperature of the fibers, whichever is the lowest for the            fiber, of        -   the fibers, followed by cooling the stack of at least two            monolayers under pressure to a temperature of 120° C. or            lower, preferably 80° C. or lower.

With this process a multilayer material sheet is obtained that has areduced liquid uptake. An additional advantage is a good stab resistanceof the multilayer material sheet increases.

High performance fibers as used in the process according to theinvention have a tensile strength of at least 1.0 GPa and a tensilemodulus of at least 40 GPa and are known per se. The fibers have anelongated shape whose length dimension is larger than their width,thickness or cross section. The term “fibers” includes a monofilament, amultifilament yarn, a tape, a strip, a thread, a staple fiber yarn andother elongate objects having a regular or irregular cross-section. In aspecial embodiment, fiber relates to an object with an elongated shapehaving a cross section aspect ratio of between 1 and 5. A cross sectionaspect ratio herein is the largest dimension of a cross section of afiber divided by the smallest dimension of a cross section of a fiber.For example a fiber with a cross section in the form of a circle has across section aspect ratio of 1. For application of the fibers inballistic-resistant articles it is essential that the fibers have a hightensile strength, a high tensile modulus and/or high energy absorption.It is preferred for the fibers to have a tensile strength of at least1.2 GPa and a tensile modulus of at least 40 GPa, more preferably thefibers to have a tensile strength of at least 2.0 GPa, even morepreferably the fibers to have a tensile strength of at least 3.0 GPa,most preferably the fibers to have a tensile strength of at least 3.6GPa.

The high performance fiber preferably contains a polymer that isselected from the group consisting of polyolefins, polyesters, polyvinylalcohols, polyacrylonitriles, polyamides, especially poly(p-phenyleneteraphthalamide), liquid crystalline polymers and ladder-like polymers,such as polybenzimidazole or polybenzoxazole, especiallypoly(1,4-phenylene-2,6-benzobisoxazole), orpoly(2,6-diimidazo[4,5-b-4′,5′-e]pyridinylene-1,4-(2,5-dihydroxy)phenylene).

In a preferably embodiment, the polyolefin comprises polyethylene andpolypropylene. Preferably the polyolefin comprises high molecular weightpolyethylene having a weight average molecular weight of at least400,000 g/mol more preferably of at least 800,000 g/mol, even morepreferably having a weight average molecular weight of at least1,200,000 g/mol, more preferably the polyolefin comprises ultra highmolecular weight polyethylene having a weight average molecular weightof at least 2,500,000 g/mol. Preferably, use is made of polyethylenefibers consisting of polyethylene filaments prepared by a gel spinningprocess as described in for example GB-A-2042414 and GB-A-2051667.

In another preferred embodiment, the high performance fiber contains apolyamide preferably based on terephthalic acid monomers, so-calledaramid fibers, such as e.g. poly(p-phenylene terephthalamide),poly(m-phenylene terephthalamide) and copolymers such asco-poly(p-phenylene terephthalamide 3,4′oxydiphenylene terephthalamide).

In the process according to the invention, the positioning of the fibersin a parallel fashion may be done by for instance pulling a number offibers from fiber bobbins on a bobbin frame over a comb so that they areoriented in a parallel fashion in one plane. Consolidation of the fibersis done so that they maintain their parallel fashion for example byembedding at least a part of the fibers in a plastic material, theplastic material in this way serving as matrix material and binding orholding the fibers together. Such embedding at least a part of thefibers in a plastic material to consolidate parallel aligned fibers intoa monolayer is well known in the art and may be done by e.g. feedingmatrix material as a solution or a dispersion to the fibers, followed bye.g. evaporating the solvent. In this way a monolayer is obtained whichmeans a layer of substantially parallel fibers being consolidated sothat they maintain their parallel fashion.

The plastic material serving as matrix material may consist of a polymermaterial, and optionally may contain fillers usually employed forpolymers. The polymer may be a thermoset or a thermoplastic or mixturesof both.

Thermosets and thermoplastics that are suitable as plastic material arelisted in for instance WO-A-91/12136 (line 26, page 15 to line 23, page21). Preferably, vinylesters, unsaturated polyesters, epoxies or phenolresins are chosen as matrix material from the group of thermosettingpolymers. These thermosetting polymers usually are in the monolayer inpartially set condition (the so-called B stage) before consolidation.From the group of thermoplastic polymers polyurethanes, polyvinyls,polyacryls, polyolefins or thermoplastic, elastomeric block copolymerssuch as polyisoprene-polyethylene-butylene-polystyrene orpolystyrene-polyisoprene-polystyrene block copolymers are preferablychosen as matrix material.

In one preferred embodiment a soft plastic is used, in particular it ispreferred for the plastic matrix material to be an elastomer with atensile modulus at 25° C. of at most 41 MPa (determined in accordancewith ASTM D638, at 25° C.) as mentioned in EP-A-0191 306 which is herebyfully incorporated by reference. Preferably, the elongation to break ofthe plastic is greater than the elongation to break of the reinforcingfibers. The elongation to break of the matrix preferably is from 3 to500%.

In another preferred embodiment a matrix material is used that containsa polyurethane. More preferably, the polyurethane is apolyetherurethane; that is based on a polyetherdiol, since that providesgood performance over a wide temperature range. In a special embodiment,the polyurethane or polyetherurethane is based on aliphaticdiisocyanates as this further improves colour stability of themultilayer material sheet.

Such a matrix material even further reduces uptake of the multilayermaterial sheet.

The content of the plastic material in the monolayer is chosensufficiently low, for example to save weight. Preferably the content ofthe plastic material is lower than 30 wt. % relative to the total weightof the monolayer. More preferably, the content is lower than 20 wt. %,even more preferably lower than 15 wt. %. Most preferably the content ofthe plastic material in the monolayer lower than 10 wt. %.

At least two of such monolayers are stacked (and rotated) such that thefiber direction in one monolayer is at an angle α, not being 0 degrees,to the direction of the fibers in an adjacent monolayer. Good resultsare achieved when this angle α is at least 30 degrees, preferably thisangle α is at least 45 degrees. More preferably this angle α is between50 and 90 degrees, even more preferably this angle α is between 75 and90 degrees.

The stack is a continuous stack meaning that the length direction is atleast 10 times the width direction, more preferably at least 30 timesthe width direction, most preferably at least 30 times the widthdirection. The stack of at least two fiber layers, preferably of atleast two monolayers preferably is interconnected e.g. throughcalendaring or otherwise at least locally adhering the at least twofiber layers or the at least two monolayers. Calendaring conditions suchas temperature and pressure are chosen sufficiently high to preventdelamination of the stack, while on the other hand not too high toprevent deterioration of fiber properties e.g. due to melting of thefiber (which may suitably be determined through known techniques such asDSC at a heating rate of 10° C./min), or in the event of non-meltingfibers the temperature at which the mechanical properties of the fibersdecreases significantly, i.e. with more than 20% (which may suitably bedetermined through known techniques such as dynamic mechanical analysisat a heating rate of 10° C./min). Such deterioration of fiber propertiesmay account for a reduced anti-ballistic performance. Typical ranges fortemperature are preferably between 75 and 155° C. in e.g. the event ofpolyethylene fibers, a typical pressure will be preferably at least 0.05MPa, whereby good conditions for temperature and pressure can be foundby the skilled person with some routine experimentation. While selectingtemperature and pressure of a calendar it should be noted that contactin a calendar is a line contact, between the 2 calendar rolls, wherebypressure and temperature are exerted on the material for a short time,typically less than 0.5 second. Local adhering may be done through e.g.stitching.

The fixation of the stack of at least two monolayers is done bysubjecting the stack to a pressure and temperature treatment for aduration of at least 2 seconds at a pressure of at least 0.5 MPa at atemperature below the melting point or degradation temperature of thefibers, followed by cooling the stack of at least two monolayers underpressure to a temperature of 80° C. or lower. Preferably the duration ofthe pressure and temperature treatment is at least 5 seconds, morepreferably the duration of the pressure and temperature treatment is atleast 10 seconds, this gives an even better reduction of liquid uptake.Even more preferably the duration of the pressure and temperaturetreatment is at least 20 seconds, most preferably the duration of thepressure and temperature treatment is at least 40 seconds. In principlethere is no limitation to the duration, but for practical reasons thiswill generally be less than 120 seconds.

In a special embodiment of the invention, interconnecting of fiberlayers and consolidation of fibers oriented in a parallel fashion in oneplane may take place during fixation. In such a way process steps b.,c., and d. of the invention may at least partly be combined. In thisembodiment at least on set of fibers oriented in a parallel fashion inone plane are fed to the fixation step together with at least onemonolayer in such a way that the fiber direction in the monolayer is atan angle α, not being 0 degrees, to the direction of the adjacent layerwith fibers. An advantage of such an embodiment is that even loweramounts of matrix material may be used.

The pressure during the fixation is at least 0.5 MPa, preferably thispressure is at least 1.0 MPa, more preferably this pressure is at least1.5 MPa, even more preferably this pressure is at least 2.0 MPa, mostpreferably this pressure is at least 2.5 MPa. Generally this pressurewill be chosen below 10 MPa, preferably below 8.0 MPa.

The temperature during the fixation should be chosen not too high inorder to prevent deterioration of fiber properties. For example forpolyethylene fibers this temperature is preferably between 75 and 145°C., more preferably between 85 and 135° C. After this treatment thestack of at least two monolayers is cooled under pressure to atemperature of 120° C. or lower, preferably 80° C. or lower, morepreferably to a temperature of 50° C. or lower. Time for cooling dependson the temperature difference between fixation temperature , e.g. 145°C. for poylethylene, and the desired temperature after cooling underpressure, e.g. 80° C. Generally this time may be at least 1 second,preferably at least 2 seconds. Typically such cooling will be achievedwithin 120 seconds.

Suitable equipment to perform the fixation step may be a belt press,preferably a belt press with a heating section followed by a coolingsection.

Preferably the belt press is a press that can apply isobaric pressures,meaning that a constant pressure that is uniformly distributed over thesurface of the stack. This pressure may suitably be applied as ahydrostatic pressure and has essentially the same value independent onthe location on the surface. A belt press that works under isobaricconditions is known per se. A suitable device for carrying out thefixation is for instance described in more detail in EP0529214, which ishereby incorporated herein by reference.

The process according to the invention may be performed in adiscontinuous manner by making separate multilayer material sheets, e.g.as produced through a drum winder, where after these sheets may besubjected to a pressure treatment according to the invention in e.g. abelt press. In the event of discontinuously produced sheets on e.g. adrum winder, preferably a continuous multilayer material sheet is madewhich may be done by e.g. slightly overlapping and adhere the abovementioned separate multilayer material sheets to form a product that canbe put on a roll. More preferably the continuous multilayer materialsheet according to the invention is made according to the process asdescribed in patent U.S. Pat. No. 5,766,725 which is hereby incorporatedby reference, combined with a fixation device in the form of e.g. a beltpress, preferably an isobaric belt press.

A multilayer material sheet comprising unidirectional high performancefibers obtainable with the process of the invention has a reduced liquiduptake when compared with known multilayer material sheets. Consequentlythe invention also relates to such multilayer material sheet comprisingunidirectional high performance fibers.

In one preferred embodiment the multilayer material sheet according tothe invention also comprises at least one plastic film. Preferably suchplastic film is adhered to one or both outer surfaces of the multilayermaterial sheet. Such adhering suitably may be done during stacking ofthe at least two monolayers, or in the fixation step of the stack of atleast two monolayers. Such plastic film permits multilayer materialsheets to slide over each other in e.g. a stack of multilayer materialsheets used for soft ballistics such as a bullet resistant vest.Therefore such multilayer material sheet may suitably be used in bulletresistant vest or other gear. This plastic film may suitably be based onpolymers chosen from polyolefins, including polypropylene, linear lowdensity polyethylene (LLDPE), ultrahigh molecular weight polyethylene(UHMWPE); polyesters, including polyethyleneterephthalate; polyamides,including polyamide 6; polycarbonate, polyurethane and comparablepolymers. Preferably use is made of LLDPE. Thickness of the films mayrange from 1-30 μm, preferably from 2-20 μm, more preferably from 3-15μm.

In another preferred embodiment the multilayer material sheet accordingto the invention may suitably be used in the manufacture of hardarticles, preferably hard ballistic articles. Examples of such articlesare panels, e.g. for armoring of vehicles, and curved articles such ashelmets and radomes. In such use the multilayer material sheet accordingto the invention preferably does not comprise a plastic film.

Test methods;

-   -   Molecular weight, Mw: Intrinsic viscosity is a measure for        molecular weight that can more easily be determined than actual        molar mass parameters like M_(w). There are several empirical        relations between IV and M_(w), but such relation is highly        dependent on molar mass distribution. In the present invention        IV is measured that relates to Mw through the equation        M_(w)=5.37×10⁴ [IV]^(1.37) (see EP 0504954 A1). An IV of 8 dl/g        would be equivalent to M_(w) of about 930 kg/mol.    -   IV: the Intrinsic Viscosity is determined according to method        PTC-179 (Hercules Inc. Rev. Apr. 29, 1982) at 135° C. in        decalin, the dissolution time being 16 hours, with DBPC as        anti-oxidant in an amount of 2 g/l solution, by extrapolating        the viscosity as measured at different concentrations to zero        concentration;    -   The melting point of a polymer is determined by DSC on a        power-compensation PerkinElmer DSC-7 instrument which is        calibrated with indium and tin with a heating rate of 10°        C./min. For calibration (two point temperature calibration) of        the DSC-7 instrument about 5 mg of indium and about 5 mg of tin        are used, both weighed in at least two decimal places. Indium is        used for both temperature and heat flow calibration; tin is used        for temperature calibration only.    -   Tensile properties (measured at 25° C.): tensile strength (or        strength), tensile modulus (or modulus) and elongation at break        (or eab) are defined and determined on multifilament yarns as        specified in ASTM D885M, using a nominal gauge length of the        fiber of 500 mm, a crosshead speed of 50%/min. On the basis of        the measured stress-strain curve the modulus is determined as        the gradient between 0.3 and 1% strain. For calculation of the        modulus and strength, the tensile forces measured are divided by        the titre, as determined by weighing 10 metres of fiber; values        in GPa are calculated assuming a density of 0.97 g/cm³. Tensile        properties of thin films were measured in accordance with ISO        1184(H).    -   Ballistic resistance: V₅₀ and Eabs were determined at 21° C.        with test procedures according to Stanag 2920, using 9 mm*19 mm        FMJ Parabellum bullets (from Dynamit Nobel). After conditioning        at 21° C. and 65% relative humidity during at least 16 hours, a        stack of sheets was fixed using flexible straps on a support        filled with Caran D'Ache backing material, which was        preconditioned at 35° C.

The invention will now be elucidated by the following examples andcomparative experiment without being limited hereto.

COMPARATIVE EXPERIMENT A

A multilayer material sheet, comprising ultra high molecular weightpolyethylene fibers manufactured by DSM Dyneema with a strength of 3.5GPa, was made by parallel aligning the fibers and adding 18 wt % of aKraton styrene-isoprene-styrene triblock copolymer as matrix. Totalweight of the monolayer was 65.5 gram. Two of such monolayers werestacked such that the fiber direction between the 2 monolayers was at anangle of 90°. At both outer surfaces a LLDPE film with a thickness of 7micrometer was added and the stack was calendared at a temperature of135° C. and a line pressure of 45 N/mm to obtain a multilayered materialsheet. Pressing time in the calendar was 0.15 second.

From this multilayer material sheet squares of 40*40 cm were cut andimmersed in a detergent solution comprising 95 wt % water and 5 wt % ofcommercially available detergent. Immersion took place during 30 minutesafter which the multilayer material sheet was wiped off with paper toweland weight gain (compared to weight before immersion) was recorded.

EXAMPLE 1

The multilayer material sheet comprising ultra high molecular weightpolyethylene fibers as made in comparative experiment A was fed througha double belt press at a pressure of 8 MPa and a temperature of 130° C.for a time of 10.5 seconds, followed by cooling under pressure to 80° C.before exiting the double belt press. Samples of 40*40 cm were cut andliquid uptake was determined in the same manner as for comparativeexperiment A.

COMPARATIVE EXPERIMENT B

A multilayer material sheet comprising cross plied monolayers ofunidirectionally aligned aramid fibers, commercially available under thename Gold Flex® 95638/AD266, was taken and samples of 40*40 cm were cut.From these samples kerosene uptake was determined by immersion inkerosene during 30 minutes after which the multilayer material sheet waswiped off with paper towel and weight gain (compared to weight beforeimmersion) was recorded. Furthermore the ballistic resistance of astack, with a total weight of 3 kilogram/m², of Gold Flex sheets wasdetermined. The ballistic resistance was determined before liquid takeup and expressed as energy absorption (Eabs) in the table below.

EXAMPLE 2

The multilayer material sheet comprising aramid fibers as used incomparative experiment B was fed through a double belt press under thefollowing conditions: a pressure of 8 MPa and a temperature of 150° C.for a time of 20 seconds, followed by cooling under pressure to 80° C.before exiting the double belt press. Again liquid uptake and ballisticresistance was determined in the same way as in comparative experimentB.

COMPARATIVE EXPERIMENT C

Example 1 is repeated whereby the multilayer material sheet is fedthrough a double belt press at a pressure of 8 MPa and a temperature of130° C. for a time of 10.5 seconds. In this experiment no cooling underpressure takes place.

The results of the tests are shown in the table below.

Sample Liquid uptake (wt %) Eabs [J*m²/kg] Comparative experiment A 9.0Example 1 4.5 Comparative experiment B 135 243 Example 2 50 261Comparative experiment C 8.0

The above table clearly shows the reduced liquid uptake of themultilayer material sheets as obtained with the process according to theinvention. Furthermore an increased ballistic resistance, expressed as ahigher Eabs, was seen.

The invention claimed is:
 1. A multilayer material sheet suitable for use in soft ballistic applications, wherein the multilayer material sheet comprises: at least two monolayers comprised of unidirectional high performance fibers with a tensile strength of at least 1.0 GPa and a tensile modulus of at least 40 GPa, and at least one plastic film positioned at an outer surface of the multilayer material sheet to allow the multilayer material sheet and an adjacent multilayer material sheet in a stack thereof to slide relative to one another, wherein the multilayer material sheet is obtained by a process comprising the steps of: (a) positioning the fibers in a parallel fashion, (b) consolidating the parallel fibers to obtain a monolayer, (c) stacking at least two monolayers such that a fiber direction in one monolayer is at an angle a relative to a direction of the fibers in an adjacent monolayer to thereby form a continuous stack, and (d) fixating the continuous stack of at least two monolayers formed by step (c) by subjecting the continuous stack of at least two monolayers for a duration of at least 2 seconds to a pressure treatment at a pressure of at least 0.5 MPa and a temperature treatment at a temperature below a melting point or degradation temperature of the fibers to thereby form a pressure and temperature treated stack of at least two fixed monolayers, and thereafter (e) subjecting the pressure and temperature treated stack of at least two fixed monolayers formed by step (d) to controllable rapid cooling under pressure to cool the stack of at least two fixed monolayers from the melting point or degradation temperature of the fibers to a temperature of 80° C. or lower within at least 2 seconds to less than 120 seconds.
 2. The multilayer material sheet of claim 1, wherein the unidirectional high performance fibers are polyolefin fibers.
 3. The multilayer material sheet of claim 1, wherein the unidirectional high performance fibers are polyethylene fibers.
 4. The multilayer material sheet according to claim 3, wherein the polyethylene fibers are ultrahigh molecular weight polyethylene fibers.
 5. The multilayer material sheet according to claim 4, wherein the at least one plastic film has a thickness between 1-30 μm.
 6. The multilayer material sheet of claim 1, wherein the unidirectional high performance fibers are aramid fibers.
 7. The multilayer material sheet according to claim 1, which further comprises an elastomeric matrix material having a tensile modulus at 25° C. of at most 41 MPa.
 8. The multilayer material sheet according to claim 1, which further comprises a matrix material which includes a polyurethane.
 9. The multilayer material sheet according to claim 1, wherein the at least one plastic film has a thickness between 1-30 μm.
 10. A soft ballistic article comprising the multilayer material sheet according to claim
 1. 11. A soft ballistic article comprising a stack of multilayer material sheets, wherein the multilayer material sheets in the stack comprise: at least two monolayers comprised of unidirectional high performance fibers with a tensile strength of at least 1.0 GPa and a tensile modulus of at least 40 GPa, and at least one plastic film positioned at an outer surface of the multilayer material sheets to allow adjacent multilayer material sheets in the stack to slide relative to one another, wherein the multilayer material sheets in the stack are obtained by a process comprising the steps of: (a) positioning the fibers in a parallel fashion, (b) consolidating the parallel fibers to obtain a monolayer, (c) stacking at least two monolayers such that a fiber direction in one monolayer is at an angle a relative to a direction of the fibers in an adjacent monolayer to thereby form a continuous stack, and (d) fixating the continuous stack of at least two monolayers formed by step (c) by subjecting the continuous stack of at least two monolayers for a duration of at least 2 seconds to a pressure treatment at a pressure of at least 0.5 MPa and a temperature treatment at a temperature below a melting point or degradation temperature of the fibers to thereby form a pressure and temperature treated stack of at least two fixed monolayers, and thereafter (e) subjecting the pressure and temperature treated stack of at least two fixed monolayers formed by step (d) to controllable rapid cooling under pressure to cool the stack of at least two fixed monolayers from the melting point or degradation temperature of the fibers to a temperature of 80° C. or lower within at least 2 seconds to less than 120 seconds.
 12. The soft ballistic article according to claim 11, wherein the unidirectional high performance fibers are polyolefin fibers.
 13. The soft ballistic article according to claim 11, wherein the unidirectional high performance fibers are polyethylene fibers.
 14. The soft ballistic article according to claim 11, wherein the unidirectional high performance fibers are aramid fibers.
 15. The soft ballistic article according to claim 13, wherein the polyethylene fibers are ultrahigh molecular weight polyethylene fibers.
 16. The soft ballistic article according to claim 15, wherein the at least one plastic film has a thickness between 1-30 μm.
 17. The soft ballistic article according to claim 11, which further comprises an elastomeric matrix material having a tensile modulus at 25° C. of at most 41 MPa.
 18. The soft ballistic article according to claim 11, which further comprises a matrix material which includes a polyurethane.
 19. The soft ballistic article according to claim 11, wherein the at least one plastic film has a thickness between 1-30 μm. 